5-arylotriazolyl-2-styryl-benzotriazoles

ABSTRACT

THE INVENTION INVOLVES NEW 5-ARYLOTRIAZOLYL 2-STYRYL BENZOTRIAZOLES OF THE FORMULA   2-((R-PHENYL)-CH=CH-),5-(4,5-(-A-)BENZOTRIAZOL-2-YL)-   BENZOTRIAZOLE   WHICH ARE USEFUL AS OPTICAL BRIGHTENING AGENTS. IN THE FORMULA R IS HYDROGEN, ALKYL, ALKOXY, CARBALKOXY, ACYLAMINO, ALKYL SULPHONYL, CARBOXY, CN, AN AMMONIUM GROUP A HYDRAZINIUM GROUP OR HALO, AND A STANDS FOR THE RESIDUAL MEMBERS OF A MONO- OR POLYNUCLEAR AROMATIC-CARBOCYCLIC RING SYSTEM WHICH IS CONDENSED AS INDICATED WITH THE HETEROCYCLIC RING AND WHICH MAY CONTAIN FURTHER SUBSTITUTENTS, WHEREAS N DENOTES THE NUMBERS 1-3. THE VARIOUS R SUBSTITUENT GROUPS MAY THEMSELVES BE FURTHER SUBSTITUTED, THE PREFERRED SUBSTITUENTS ON THE ALKYL GROUPS BEING OH, CN, HALO, ALKOXY, CARBALKOXYL AND CARBOXYL GROUPS.

3,595,859 -ARYLOTRIAZQLYL-2-STYRYL- BENZOTRIAZOLES Carl-Wolfgang Schellhammer, Opladen, and Wolf-Dieter Wirth, Cologne-Stammheim, Germany, assignors to Farbenfabrilren Bayer Aktiengesellschaft, Leverlrusen, Germany No Drawing. Filed Apr. 8, 1968, Ser. No. 719,722 Claims priority, applicg tigzn lGtlarmauy, Apr. 17, 1967,

Int. Cl. covd 55/04 Us. Cl. 260-240 7 Claims ABSTRACT OF THE DISCLOSURE The invention involves new S-arylotriazolyl 2-styryl benzotriazoles of the formula The object of the present application comprises valuable new 5-arylotriazolyl-Z-styryl-benzotriazoles of the formula which are eminently suitable as brightening agents. In the general formula, R stands for hydrogen or a substituent, for example, an alkyl group, an alkoxy group, a carbalkoxy group, an acylamino group, an alkylsulphonyl group, a carboxylgroup, a CN-group, an ammonium group, a hydrazinium group, or halogen, and A stands for the residual members of a monoor polynuclear aro matic-carbocyclic ring system which is condensed as indicated with the heterocyclic ring and which may contain further substituents, whereas n denotes the numbers 1-3. The alkyl, alkoxy, carbalkoxy, acylamino and alkylsul-, phonyl groups may'be further substituted, the preferred substituents in the case of alkyl groups being OH, CN, halogen, such as Cl and Br, alkoxy groups, carbalkoxy groups and carboxyl groups. Suitable alkyl radicals R are, for example, CH 0 H nC,H-,, n-CJ-l, iso-CJ-I, and tert.C,I-l,; suitable alkoxy radicals R are, for example, OCH;, OC H, and 00 1-1 Examples of carbalkoxy groups R are the radicals COOCH,, -CO0C H, and COOC,H,. Suitable halogen radicals are, in particular, Cl and Br, suitable acylamino radicals are mainly formylamino, alkylcarbonylamino, arylcarbonylamino, aralkylcarbonylamino, alkylsulphonylamino,

i arylsulphonylamino and aralkylsulphonylamino radicals,

r md

' 3,595,859 "Patented July. 27,1971

2 for example the radicals --NHCO CH,, NHCOC,H NHCOC H NHSO,CH,, --NHSO,C,H v and NHSO,C,H,Cl-l,

Suitable alkylsulphonyl radicals R are, for example, SOgCH3, SO C;H and S0:C3H1-:

Suitable ammonium radicals are, for example, trialkylammonium radicals, such'as ice fiwmnx l 6)t suitable hydrazim'um radicals are,.for example,

CH; I INH,X

can -I l-NHex 61H where X stands for an anion, for example,-.for Cl Br CH3OSO3G, C3H50So3 0r suitable dialkylamino groups are especially-those thealk'yl' radicals of which contain 1-4 carbon atoms.

Preferred compounds are those of the formulav (Ia) wherein R and A have the meaning; given above.

The new S-arylotriazolyl-2-sty 'y1-bcnz0triazoles can-be,

obtained by triazolisation of o-amihoazo-styryl-benzotriazoles of the formula N N=N *1 {I NH,

in which A stands for the residual members of a monoor polynuclear aromatic-carbocyclic-rriag system which is fused in the indicated manner with the heterocyclic ring and which may contain further sulistituents; R stands for hydrogen or a substituent and n denotes the numbers 1-3.

If desired, the substituents R or .tHe substituentspresent in the fused monoor polynuclcar Larornatic-carbocyclic ring systems may be further modified after triazolis'ation, for example, a dialkylamino group may bC'OOHVCflQd into a quaternary ammonium group or a carboxyl group an ester group.

Triazolisation is carried out in known manper, for example, by oxidation with coppe r(II) .salts, .ifJdesired, in,

the presence of air or with sodium hypochlorite.

The o-aminoazo-styryl-benzotriazoles of the Formal II can be obtained, for example, by reacting'chloroacetic acid with S-nitro-benzotriazole in water, in the presence of alkali, at an elevated temperature to form 5-nitrobenzotriamle-Z-acetic acid, further reaction-with aromatic A aldehydes in the presence of catalytic'amounts of piperidine at -200 C.- to form 5-nitro-2-styryl-benzotriazoles and subsequent reduction to S-amino-Z-styryl-benzotriamles of the formula (III) in which R and n have the same meaning as above, diazotisation and coupling with monoor polynuclear primary aroamtic-carbocyclic amines which couple in the o-pos'ition to the NH; oup.

Suitable aromatic a ehydes for the preparation of the s-nitro-2-styryl benzotriazoles are, for example, benzaldehyde, p-methylbenzaldehyde, p-tert.-butyl-benzaldehyde, p-methylsulphonyl-benialdehyde, p-dimethylamino-benzaldehyde, p-cyano-benzaldehyde, p-carboxy-benzaldehyde, p-carbethoxy-benzaldchyde, p-chloro-benzaldehyde, pbromo-benzaldchyde, 2 -chlorobenzaldehyde, Z-methoxybenzaldehyde, 2,4-dichloro 'benzaldehyde, 2,4,5-trichlorobenz'aldehyde and 4-acetylamino benzaldehyde.

Monoor polynuclear primary aromatic-carbocyclic amines which are suitable coupling components for the preparation of the o-aminoazo compounds are, for example,

rn-phenylene-diamine, N,Ndimethyl-m-phenylene-diamine, 4-amino-2-methoxy-toluene, 4-amino-Z-n-butoxy-toluene, 4-amino-2-n-dodecyloxy-toluene, Lamina-naphthalene, 2-amino-6-methoxy-naphthalene and S-amino-acenaphthene.

The new products of the Formula I are valuable bluefluorescent brightening agents. The object of the invention, therefore, also comprises brightening agents containing 5 -arylotria zolyl-Z-styryl-benzotriazoles according to Formula I as active ingredient.

Compounds which are particularly suitable as brightening agents are those of the formulae in which R stands for hydrogen, analkyl, all'roxy or ammonium group, especially agroup CH,,.OCH or iiwmnx where X denotes an anion.

Thenew compounds of the Formula I are especially suitable for the brightening of synthetic materials, such as the brightening of fibres, filaments, fabrics, foils or plastic materials of aromatic polyesters, such as polyethylene glycol terephthalates and aromatic polyesters obtained from terephthalic acid and l,4-bis-hydroxymethyl-cyclohexane, of polymers and copolymers based on acrylonitrile or as.-dicyanoethylene, polyvinyl chloride, cellulose Z A-acetate, and cellulose triacetate, and for the brightening of lacquers of cellulose acetates. Application of the brightening agents which contain the compounds of the Formula I in pure form or mixed with other suitable additives, is carried out in the usual manner, for example, in the form of aqueous dispersions or in the form of solutions in organic solvents, such as acetone, ethyl acetate, glycol monomethyl ether acetate, methylene chloride or toluene. If desired, the brightening agents can be applied in combination with detergents or they may be added to casting materials serving for the production of foils or filaments.

The amounts of compounds of the Formula I required for the application of a brightening agent can easily be established in every case by preliminary experiments. In general, amounts of 0.1 to 0.5%, referred to the material to be brightened, will prove sufiicient.

With the new products used as brightening agents, eminently clear white shades, very good fastness to light and, in particular, a high fastness to chlorite can be achieved on the materials thus brightened.

The parts given in the examples are parts by weight, the percentages are percent by weight.

EXAMPLE 1 Fabrics of polyethylene terephthalate fibres, which have a yellowish appearance, are washed at 75 C. with a commercial detergent containing about 20% of synthetic surface-active substances and, if desired, complex phosphates, sodium silicate, carboxymethyl cellulose, as well as sodium perborate and, in addition, 0.2% 5-(naphtho-[2,1-

, d]-triazolyl-2)-styryl-benzotriazole. After rinsing and drying, the laundry goods have a bright white appearance.

The 5- (naphtho- 2, l-d] -triazolyl-2' -2-styryl-benzotriazole used above is prepared in the following manner:

19.4 g. of the o-aminoazo dyestulf obtained from diazotised S-amino-2-styryl-benzotria2.ole and fi-naphthylamine are heated in 300 ml. pyridine containing 20 g. of copper(II)-acetate at boiling temperature for 1 hour while stirring. After cooling, the precipitated product is filtered off with suction, washed with some alcohol and recrystallised from dimethyl formamide or glacial acetic acid. Small pale yellow crystals are obtained which melt at 197 C.

The o-aminoazo dyestufi was obtained as follows:

The 5-nitro-2-styryl-benzotriazole which can be obtained by condensation of S-nitro-benzotriazole with chloroacetic acid to form 5-nitro-benzotriazole-2-acetic acid, followed by condensation with benzaldehyde in the presence of piperidine at 160-170 C., is catalytically reduced to 5-amino-Z-styryl-benzotriazole of melting point 154- 156 C.

11.8 g. (0.05 mole) 5-amino-2-styryl-benzotriazole are diazotised in a hydrochloric acid solution at 0 C. with 3.5 g. (0.05 mole) sodium nitrite. The diazotisation mixture is subsequently added to a solution of 7.2 g. (0.05 mole (fi-naphthylamine in ml. glacial acetic acid, mixed with 20 g. of crystalline sodium acetate and stirred at 20 C. for several hours. A red dyestuff is thus precipitated, which is filtered off with suction, washed with water and dried.

When the o-aminoazo-styryl-benzotriazoles obtained by coupling diazotised 5-amino-Z-styryl-benzotriazole with 2- methoxy-4-aminotoluene or 2-n-butoxy-4-aminotoluene are oxidised in the manner described above, then there are obtained 5-[5'-methyl-6'-methoxy-benzotriazolyl-2']- styryl-benzotriazole of melting point ZZZ-223 C. and 5 5 '-methyl-6'-butoxy-benzotriazolyl-2'] -styryl-benzotriazole of melting point 151-153 C., respectively.

EXAMPLE 2 sulphonate, 0.75g. formic acid and 0.1 g. 5-(naphth'o-.

[2,l-d]-triazolyl-2)-2-(p methyl styryl)-benzotriazole; the bath is then heated to boiling point within 30 minutes and held at boiling temperature for about 45 minutes, while the fabric is moderately agitated in the bath. The fabric is subsequently rinsed and dried. The fabric is then excellently brightened.

The brightening agent used above is prepared in the following manner:

The o-amioazo-styryl-benzotriazole which can be obtained bycoupling 1 mole of diazotised S-an ino-Z-(pmethyl styryU-benzotriazole with 1 mole fl-naphthylamine is oxidised as described in Example 1, whereby clear yellowish crystals of melting point 21l- -223 C. are obtained.

The S-amino-Z-(p-methyl-styryl)-benzotriazole used as starting material is obtained as follows:

345 g. S-nitro-f nzotriazole-Z-acetic acid, prepared accordingto Example 1, were condensed at ISO-155 C. for 5 hours in the presence of catalytic amounts of piperidine with 200 g. prmethyl-benzaldehyde. The S-n'itro-Z-(pmethyl-styryl)-be hzotriazole of melting point 213- C. thus obtained is reduced with tin(lI)-chloride in gladal acetic acid to S-amino-Z-(pmethyl styryl) benzotriazole of melting point l69-l71 C. The diazotisation was carried out as described in Example 1. P

EXAMPLE 3 A fabric of cellulose acetate fibres is introduced in a liquor ratio of 1:40 at 60 C. into an aqueous b'ath containing, per litre, 1 g. oleyl sulphonate, 0.95 g. foi'amic acid and 0.075 g. S-(naphtho-[2,1-d]-triazolyl-2')-(p-methoxy-styryD-berizotriazole. After 45 minutes, the fabric is rinsed and dried. 'It is well brightened.

The brightening agent used above is prepared in the following manner:

The 5-nitro-2'-' (p-methoxy-styryl)-benzotriazole of melting point 239-.2 41 C. which can be obtained by condensation of S -nitro-benzotriazole-Z-acetic acid with 4- methoxy-bcnzaldehyde is reduced in butanol with iron powder/hydrochloric acid to S-amino-Z-(p-methoxystyryl)-benzotr iazole. 0.05 mole of theamine so obtained are diazotised as described in Example 1, coupled with 0.05 mole fi-na'phthylamine and subsequently oxidised with copper(II)I-acetate in pyridine to form S-(naphtho- [2,l-d]-triaz.olyl 2')-2-(p-methoxystyryl)-benzotriazole of melting point l88-l90 C.

EXAMPLE 4 1. 5-benzotrlbzolyl-2-styryl-benzotriazole of the for-- mula in which R; stands for hydrogen, lower alkyl, lower alkoxy or ammonium or tri-lower alkyl ammonium, R is lower alkyl audit" is lower alko'xy and -n is a number from 1 to 3.

6 2. 5-arylotriazolyl-Z-styryl-benzotriazole of the formula N A l N-- NCH=CH(R)- N from the group consisting of lower alkyl; lower alkoxy:

carb lower alkoxy; acylamino selected from the group consisting of Nl-IXR, wherein X is CO or SO, and R, is lower alkyl, hydrogen, phenyl, or tolyl; lower alkyl sulphonyl; carboxyl; cyano; ammonium; tri lower alkyl ammonium; hydrazinium; di lower alkyl hydrazinium; halogen, wherein the alkyl groups of the said substituent may contain substituents selected from the group consisting of hydroxy, cyano, halogen, lower alkoxy, carbo lower alkoxy and carboxyl group; a denotes a member selected from the group consisting of phenylene, naphthylene, and acenaphthylene wherein the said member A may contain substituents selected from the group consisting of lower alkyl; lower alkoxy; acylamino selected from the group consisting of NHXR, wherein X is CO or SO, and R, is lower alkyl, hydrogen, phenyl, or tolyl; and di lower alkyl amino wherein the alkyl groups of these substituents may further contain substituents selected from the group consisting of hydroxy, cyano, halogen, lower alkoxy, carbo lower alkoxy and carboxyl groups; and wherein n stands for a number from 1 to 3.

3. 5-naphthotriazolyl-Z-styryl-benzotriazole of the formula 4. 5-(5-methyl-6' n butoxy benzotriazolyl 2 (pmethyl-styryl)-benzotriazole of the formula CHr- D-ClHgO 5. ,S-(Sf-methyl 6' methoxy-benzotriazolyl) 2 (pmethoxystyryD-benzotriazole of the formula CHr- 7 7. 5-naphthotriazolyl-Z-styryl-benzotriazole of claim 2 References Cited fmmla UNITED STATES PATEN S 2,462,405 2/1949 Keller et a1 260240X 2,715,630 8/1955 Sartori 260-304 5 FOREIGN PATENTS R ll OTHER REFERENCES 10 Chemical Abstracts, vol. 58, cols. 3077 to 3078 (1963). N

JOHN D. RANDOLPH, Primary Examiner in which R; stands for hydrogen, an alkyl, alkoxy or am- U S cl X R monium group and in which the naphthalene radical may be substituted as stated in claim 2 wherein n stands for [5 106-176; ll733.5; 252-402, 301.2; 260-75, 88.7, the number 1-3. 92.8, 157, 240.9

1,456,745 9/ 1966 France 260-240 

